TY - JOUR
T1 - Sulfoxides as Response Elements for Fluorescent Chemosensors: Does It Work?
AU - Chen , Jun-Sheng
AU - Zhao , Li
AU - Yang , Yang
AU - Chu , Tian-Shu
JO - Journal of Atomic and Molecular Sciences
VL - 1
SP - 1
EP - 10
PY - 2015
DA - 2015/06
SN - 6
DO - http://doi.org/10.4208/jams.120214.013115a
UR - https://global-sci.org/intro/article_detail/jams/8175.html
KW - Fluorescent probes, Sensing mechanism, Density functional calculations, Intramolecular charge transfer (ICT), sulfoxide moiety.
AB - <p style="text-align: justify;">Our density functional theory (DFT)/time-dependent DFT (TDDFT) calculations
for the sensing mechanism of a series of sulfoxide based metal-responsive fluorescent
chemosensors, suggested that the intramolecular charge transfer (ICT) is not a
reasonable mechanism for these chemosensors. The calculated electronic transition energies,
the corresponding oscillator strengths of these chemosensors and the involving
frontier molecular orbital analysis indicated that there is no obviously ICT state with
a transition oscillator strength approaching to zero. The fluorescence quenching of
these chemosensors cannot be explained by ICT process. The ground state optimized
structures of chemosensors and their complexes indicated that there might be twisted
excited configuration for these chemosensors and the twisted excited state configuration
may response for the fluorescence quenching. The configuration change can be
blocked in the Zn complex that is responsible for these complexes showing fluorescence
emission enhancement. In order to understand the function of the sulfoxides
group in these metal-responsive fluorescent chemosensors, excited state configuration
optimization as well as the excited state hydrogen bond effect on the fluorescence enhancement
in the aqueous solvent will be conducted.</p>